Ester-like derivatives of azo dyestuffs



Patented Jan. 24, 1950 ESTER-LIKE DERIVATIVES OF AZO DYESTUFFS Friedrich Felix and Alphonse Heckendorn, Basel,

Ernst Reich, Neue Welt, and Fritz Oesterleim Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application September '20, 1-945, Serial No. 617,699. In Switzerland October 6,

2 Claims. 1'

U. 5.. Patents Nos. 21702632, 2120;741', 2,199,048 and 2,276,187 describe the preparation of esterlike dyestuff derivativeshyttreating;dyestuffs-containing hydroxyl groups with organic acylating agents which ,containfin addition tothe-acylatinggroup, at least one 'substituent' which; if necessary after. suitable conversion, imparts solubilitytothe acylation products. Theseesterificationproducts have hitherto beenused principally for dyeing cellulosic materials (of; U. TSL, Patent'No. 2,095; 600);

Application Serial-No. 617,607, filed on even date herewith, demonstrates that estersobtained according to the process of U. S. Patents Nos. 2,170,262, 2,120,741, 2,199,048 and 2,276,187, can surprisingly he used with good results for chroming animal fibers if the dyeing is conducted in the presence of ammonium sulfate and analkali chromate.

The object of'ithepre'sen't' invention is to pro duce new esters which are especially suitable for dyeing animal lfiboers by the-process of application Serial No. 617,697. These esters are derived principally from ortho ortho-dihydroxyazo dyestufis obtained from aromatic ontho-hydnoxylated diazo compounds and aromatic or heterocyclic hydroxyl compounds which couple in orthoposition with respect to the hydroxyl group, the two components being-so selected that the resulting ortho :ortho!-=dihydroxyazo:dyestufi, if it contains-no nitro groups, will contain at least two substituents whiohdo notoimpant solubility. In the latter case the resultant dyestuffs are subsequently nitrated. Thus,,the dyestuifs are produced by an appropriate combination of diazo compounds, which are made, for example, from the ortho-aminophenols or ortho-aminonaphthols or analoques thereof hereinafter mentioned; with coupling components of the type of the hydroxy compounds also mentioned hereinafter.

There may be used as ortho=aniinophenols, among others:I1-hydroxy 2=amin0benzcna l-hydroxy Z-amino 4-chlorobenzene, il-hydroxy- 2-amino-4:fi dichlorobenzemf '1-hydroxy-2-amino-3 4 6 -trichlorobenzene, -1'hydroxy-2 -aminochloronaphthalene. '1-hydroxy-5-chloronaphthalene, '2-hydroxy-6-methoxynaphthal ene,, 2 hydroxy-7 methoxynaphthalene, 2-hyclroxy-4t6-dichloronaphthalene, 2-hydroxy-4 tfi-dibromonaphthalene,l-hydroxy--methoxynaphthalene, -1-hydroxynaphthalene 4 methylketone, '1 -;hydroxy'- naphthalene-.4-phenylketone-, l-jhydroxy-si-ethylnaphthalene; also arylides of 2:3-hydroxynap'hthoic acid, such as the condensation products of this acid with amino compounds, such as 1- aminobenzene, 1 -amino-2-.1methoxybenzene, 4- amino-,1:1-azobenzene,; etc, also, compounds offlthe benzene series, such as l-hydroxy-emethylbenzene, 1ehydrQ y-Z1al1y1-4-methylbenzene, 1-1157.- droxy-2an-propylr4-methylbenzene,. ,l-hydroxy 2.-isopropy1-.4emethylbenzene, I-hydrOXy-Z-Qhen- 25 1- .4 methylbenzene, -1-hydroxy2-methyl-4- ethylbenzene, l -hydr'oxye2 -,ethyl 4 me.thy1benzene, 1-hydroxy-2amethy1-4aisopropylbenzene. 1-: hydroxy 2 methyl-4-oyc1ohexylbenzene, .l -hydroxy-2-methyl-4-henzylbenzene, 1 hydroXY-Z- benzyl-4-napropylbenzene etc.

Hydrdxyl compoundsare also to be understood to mean compounds containing .enolizalolev keto F groups,.such as, for instance, 3-,methyl-.5 -pyrazo- 5! -dichloro) -phenyle3-methyl-5 pyrazolone, 1'.-

(-3 achloro)--pheny1s3emethylq5-pyrazolone,. 1- (Binitro) -.phenyl-.3-,methyl-5-pyrazo1one, 2 :4-.di

hydroxyquinoline, the .anilide of ,acetoacetic ,acid, theortho-anisidide of automatic .acid, the 2:4,-

dichloroanilidc of acetoacetic acidyetc. 'Iihe azodyestuffs resulting from these components under the conditions indicated are thus esterified with the esterifying agents of Patents Nos. 2,170,262, 2,120,741, 2,199,048 and 2,276,187 such as, -for example benzoylchloride sulfonic -acid',-benzoic acid- 3-sulfochloride dichloride of aneta-sulfobenzoic acid, benzoic' acid-3:5-disu1fb-chloride, sulfosalicylic acid dichloride, sulfo-aceticacid chloride, 4- chloromethylbenzoylchloride, etc, advantageously in the presence of a tertiary'base, such as pyridine or thiazole.

The new dyestuffs thusroorrespond to the generalformula 3:4 5 G-tetrachlorobenzene, 1-hydroxy-2-aminoy,-'(3- -R1--N =N.-Rz- 0L-z in which the symbol y--O- is in ortho-position to the azo group and they symbol -Oz in an adjacent position to thegazo group,

-R1-N=N-Rz stands for they radical of ,an azo compound :in

which BL represents an aromatic radicalyselected from the aromatic radicals of; the benzene and of the naphthalene series, and R2 stands for the radical of a coupling component, R1 and R2 being free from substituents which impart water-solubility but containing at least two other substituents, y standing for an acyl radical containing at least one salt-forming group selected from the group consisting of the radical of a quaternary ammonium group and of a sulfonic group, and z for a member of the group consisting of hydrogen and an acyl radical containing at least one salt-forming group selected from the group conv sisting of the radical of a quaternary ammonium group and of a sulfonic group;

The esterification products may be worked up in such a manner that after the reaction is completed, the tertiary base is distilled off under reduced pressure and the residue is transferred into a salt solution, whereby the esterification products are separated.

, The latter may also beobtained in the form of more diiilcultly soluble double salts, for instance zinc double salts, if a suitable metal chloride, such as, for instance, zinc chloride or inorganic or organic acids are added, to the original reaction mixture.

a The following examples illustrate the inven-. tion, but are not to be regarded as limiting it in any way, the parts being by weight:

Example 1 36 parts of the azo-dyestufi obtained from diazotized 1-hydroxy-2-amino-4-chlorobenzene and 1-hydroxy-5:8-dichloronaphthalene are esterified as follows: 44-60 parts of benzoic acid 3-sulfochloride are first dissolved in about 180 parts of pyridine at 50-60 C. Then, at about 40 (1., the 36 parts of the aforesaid azo-dyestufl are added while thoroughly stirring. After the stirring operation has continued at approxiinately 50 C. for several hours, the pyridine is 40 distilled oiT under reduced pressure, the mass is introduced into about 500 parts of a sodium chloride solution of per cent. strength and the whole is stirred until the dyestufl is homogeneously dispersed in the solution. The dyestuff is then filtered off, washed with sodium chloride solution and dried in a vacuum. It is a yellowbrown powder which easily dissolves in water and which by the single bath process in the presence of agents yielding chromium, dyes wool reddish blue tints. In its free form the dyestufl probably corresponds to the formula G1 I I sodium chloride solution, stirring, filtering and drying, a yellow-brown powder is obtained which easily dissolves in water and which, by the single bath process in the presence of agents yielding chromium, dyes wool pure blue tints. In its free form the dyestuff probably corresponds to the 'formula 502K 80211 O I Y i 0 c1- N=N The following procedure may alternatively be applied: 60 parts of benzoic acid-3-sulfochloride and 40 parts of the azo-dyestuff are stirred for 3 hours at a temperature of 40-4 5" C. in 200 parts of pyridine, the pyridine is distilled ofi under reduced pressure, the remainder is introduced 5 into 1000 parts of water and the ester is filtered. This is then stirred in 1000 parts of a sodium chloride solution of 5 per cent. strength, filtered and dried.

When using, instead of the 44-60 parts of benzoic acid-3-sulfochloride, the corresponding quantity of benzoic acid-3:5-disulfochloride, there is obtained a dyestuif of the formula 0 SIOI 35 sonar 01 401K HOs 45 whereas products of the formula 0 son; o-t

on 01 son:

or N=N are obtained when using smaller quantities of this esterifying agent.

The similarly prepared ester of the dyestufl ootained from. diazotized 1-hydroxy-2-amino 3 z 4 6 -trichlorobenzene and 1-hydroxy-5 8-di-. chloronaphthalene" is suitable also for dyeingfam,

cording to the after-chromin'g'procss.

smegm 58 parts of. benzoic acid-3-su1iochloride are dissolved in-150 parts: of pyridine and 32.85 parts of the azo-dyestuffi obtained from diazotized 1-hydroxy-2-aminoe chlorobenzene and .l-hydroxy-4-methoxynaphthalene are introduced at 40-50" C. while thoroughly stirring; This mixture is stirred for 2-3. hours, after whichrtime the pyridine is distilled off in a vacuum. and the residue is introduced into 500 parts of a sodium chloride solution of 10 -per cent. strength. The precipitated-dyestuir' is filtered off, washed with sodium chloride solution andydr-ied. It is a dark powder which dissolyes in waterand the solution of which dyeswool.accordingtothe single bath process in the'presence' of "agents yielding chromium: blue tints. In its-freeform. zthe adyestufl probably corresponds to the formula;

Example 45.5 parts. of the dyestuffobtained fifom;d1- azotized I hydroxy-2'-amirro- 4 chlorobenzene and 2-hydroxy-4:fi-dibronro naphthalene are dissolved in 160 parts of pyridine and 58 parts of benzoic acid-S-sulfochloride are added while thoroughly stirring. This mixture is stirred at about 50 C. until a test portion is easily soluble in water. After the dyestuff has been worked up in accordance with the procedure described in Example 3, a dark powder is obtained which is easily soluble in water and dyes wool according to the single bath process from an aqueous solution in the presence of agents yielding chromium fast reddish-blue tints. In its free form the dyestufi probably corresponds to the formula f Oar- HQ N=N Br By applying a similar procedure to the dyestuffs obtained from diazotized 1-hydr0xy-2- aminobenzene and 2-hydroxy 4:6 dibromonaphthalene, a product showing similar behavoir is obtained.

Example 5 35.0 parts of the dyestuif obtained from diazotized 1-hydroXy-2-amino-4 6 -dichlorobenzene and 2:4-dihydroxyquinoline are treated in 150 parts of pyridine with 38 parts of benzoic acid- 3:5-disulfochloride until a test portion of this mixture is easily soluble in water. The dyestuif is isolated by distilling oil the pyridine under reduced pressure, introduction of the mass into sodium chloride solution, filtering and drying. It dyes wool from an aqueous solution in the presence of an agent yielding chromium bordeauxred tints. In its free form the dyestuff probably corresponds to the formula m A similar procedure is followed in esterifying the dyestufi obtained from diazotized i-hydroxy- 2-amino-4-chlorobenzene and 1-(2-chloro)- phenyl-S-methyh5=pyrazolone; whereby a dyestuff is obtained which dyeawool according to the sameprocessredrtints.

Ame-dyestuffs,ofitheformulas Cl N=N-.-oHo. 303

may also be treated with acylating agents, whereby compounds of the formulas Hi l respectively, are obtained.

66 Example 6 7 F another hour at the boil. The wool is then rinsed and dried. It is dyed a fast pure blue tint.

What we claim is: 1. An ester-like monoazo dyestufl. derivative which corresponds to the formula in which the radical is in the ortho-position to the azo group and the symbol 0Z in a position adjacent to the azo group, R1N=NR.2 stands for the radical of an azo compound in which R1 represents an aromatic radical of the benzene series and R2 stands for an aromatic radical of the naphthalene series, R1 and R2 being free from substituents which impart water-solubility but containing together at least two halogen atoms as substituents, z standing for a member of the group consisting of hydrogen and the radical 2. The ester-like azo-dyestufi derivative of the formula 0 503K 0 BOI i C n C O 0 CGl o1 N=N FRIEDRICH FELIX. ALPHONSE HECKENDORN. ERNST REICH. FRITZ OESTERLEIN.

, REFERENCES CITED The following references are of record in the file of this patent: UNITED STATES PATENTS Number Name Date 2,095,077 Payne Oct. 5, 1937 2,095,600 Graenacher et a1. Oct. 12, 1937 2,109,806 Straub et a1 Mar. 1, 1938 2,120,741 Graenacher et al. June 14, 1938 2,170,262 Graenacher et al. Aug. 22, 1939 2,199,048 Graenacher et al. Apr. 30, 1940 2,237,483 Graenacher et al. Apr. 8, 1941 2,249,956 Heyna July 22, 1941 2,274,544 Gubelmann Feb. 24, 1942 2,276,187 Graenacher et a1. Mar. 10, 1942 Linch Oct. 10, 1944 Certificate of Correction Patent No. 2,495,244 January 24, '1950 FRIEDRICH FELIX ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 12, for the serial number 617,607 read 617,697; line 38, for analoques read analogues; column 2, line 29, for (B'nitro) read (8'-m'tr0); column 7, line 17, for -0-Z read 0z;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 6th day of June, A. D. 1950.

[sun] THOMAS F. MURPHY,

Assistant C'ommz'ssz'oner of Patents. 

1. AN ESTER-LIKE MONOAZO DYESTUFF DERIVATIVE WHICH CORRESPONDS TO THE FORMULA 